With the development of digital technology, electronic devices such as mobile information devices and home information appliances have become increasingly highly functional in recent years. Thus, we have seen a rise in the demand for nonvolatile memory elements which have larger capacity, allow power reduction in writing, reduce writing and reading time, and have longer operating life.
It is said that miniaturization of flash memories using existing floating gates has a limit to meet such a demand. On the other hand, in the case of a variable resistance nonvolatile memory element in which a variable resistance layer is used as a material of a memory unit, it is possible to form the variable resistance nonvolatile memory element with a memory element having a simple structure in which the variable resistance layer is placed between an upper electrode and a lower electrode, and thus there are expectations for further miniaturization, reduction in writing and reading time, and low power consumption.
For instance, a nonvolatile memory element has been proposed which creates a high resistance state and a low resistance state by implanting and extracting metal ions through application of voltage between an upper electrode and a lower electrode and which stores data by assigning a numerical value to each of the states (refer to Patent Literature 1, for example). Furthermore, a nonvolatile memory element has been proposed which is called a phase-change memory and in which a resistance state of a resistant variable layer is changed by changing a crystalline state of the variable resistance layer with electrical pulses (refer to Patent Literature 2, for instance).
Moreover, in addition to the above, a variable resistance nonvolatile memory element has been proposed in which a variable resistance layer is made of a metal oxide. Such a nonvolatile memory element is largely divided into two types depending on a material used for the variable resistance layer. One of the types is a variable resistance nonvolatile memory element which is disclosed in Patent Literature 3 and the like and in which a variable resistance layer is made of a perovskite material (Pr1-xCaxMnO3 (PCMO), La1-xSrxMnO3 (LSMO), GdBaCoxOy (GBCO), or the like).
Furthermore, the other type is a variable resistance nonvolatile memory element in which a variable resistance layer is made of a binary transition metal oxide. The binary transition metal oxide has very simple composition and structure in comparison with the above perovskite material, and thus it is easy to perform composition control and film formation at the time of manufacture. On top of that, the binary transition metal oxide has an advantage that compatibility with a semiconductor fabrication process is relatively favorable, and many researches on the binary transistor metal oxide have been conducted in recent years. For example, Patent Literature 4 and Non Patent Literature 1 disclose NiO, V2O5, ZnO, Nb2O5, TiO2, WO3, CoO as variable resistance materials. Moreover, Patent Literature 5 discloses a variable resistance nonvolatile memory element in which a suboxide (oxide deviating from stoichiometric composition) such as Ni, Ti, Hf, Nb, Zn, W, and Co is used as a variable resistance material. In addition, an example has been proposed where a structure in which the surface of TiN is oxidized and a TiO2 crystalline film in nanometer order is formed is used for a variable resistance layer (refer to Patent Literature 6 and Non Patent Literature 2, for instance).
Furthermore, a so-called one-time programmable memory has been proposed in which a titanium oxide and a tantalum oxide (Ta2O5) are used as variable resistance materials and which allows one-time writing (refer to Patent Literature 7, for example).